Azo compounds and material colored therewith



Patented July 6, 1943 UNTTED STATES PATENT OFFICE AZO COMPOUNDS AND MATERIAL COLORED THlE-REWITH Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application July 21, 1941,

Serial No. 403,359

(Cl. 26ll155) 15 Claims.

lose butyrate and the hydrolyzed as well as the unhydrolyzed mixed organic acid esters of cellulose such as cellulose acetate-proprionate, cellulose acetate-butyrate, and the cellulose ethers such as methyl cellulose, ethyl cellulose, or benzyl cellulose While our invention will be illustrated more particularly in connection with the coloration of cellulose acetate, a material to which the invention is especially adapted, it will be understood that it applies equally to the coloration of the other materials just mentioned.

It is an object of our invention to provide a new class of azo dyes. Another object of our invention is to provide colored textile materials which possess excellent fastness to light, excellent resistance to burnt gas fumes, good fastness to washing and which are easily dischargeable to a pure white. A further object is to provide a process for the coloration of textile materials such as organic derivative of cellulose, wool, silk, Nylon and Vinyon textile materials. Other objects appear herein.

The azo compounds of our invention by means of which the above objects are accomplished or made possible consist of the azo compounds having the formula:

wherein X stands for a member selected from the group consisting of an alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group, and R1 stands for a member selected from the group consisting of a l-alkyl-Z-l-ow carbon alkyl tetrahydroquinoline nucleus and a 1-alkyl-2-low carbon alkyl phenmorpholine nucleus, said tetrahydroquinoline and phenmorpholine nuclei being joined to the azo bond shown through the carbon atom in the 6-position.

While our invention relates broadly to the azo compounds havin the above formula, it relates. more particularly to the azo compounds having the formula:

wherein Q stands for a member selected from the group consisting of O and CH2 and Y and Y1 each stand for a member selected from the group con-v sisting of hydrogen, a low carbon alkyl hydrocarbon group, and a halogen atom.

, The alkyl group attached to the nitrogen atom forming a part of the tetrahydroquinoline and phenmorpholine nucleus is ordinarily an alkyl group such as methyl, ethyl, propyl, butyl, ,B-hydroxyethyl, p-hydroxypropyl, c -dihydroxyprm pyl, 'y-hy-droxypropyl, t-hydroxybutyl, c-sulfoethyl, fi-sulfatoethyl, ,fl-methyl-fip dihydroxypropyl and pentaerythrityl, for'example. Similarly, by a low carbon alkyl group we refer more particularly to groups such as methyl, ethyl, propyl, butyl, and c-hydroxyethyl.

Compounds wherein the alkyl group in the 2- position of the phenmorpholine and tetrahydroquinoline nuclei is methyl have been found particularly advantageous. Likewise, compounds wherein the alkyl group attached to the nitrogen atom of the phenmorpholine and tetrahydroquinoline nuclei is a hydroxyalkyl group appear to be generally advantageous, and of these 18,7- dihydroxypropyl and B-methyl-fifl-dihydroxy- P DY appe r to be most advantageous. Similarly, the presence of a methyl group in the!- position of the phenmorpholine and tetrahydroquinoline nuclei appears to be beneficial.

Similarly, in the interest of clarity, it is here noted that the tetrahydroquinoline and phenmorpholine nuclei are numbered as indicated hereinafter.

Tetrahydroquinoline H2 l6\5/\ 4 H:

Phenmorph oline The azo compounds of our invention constitute valuable dyes for the coloration of the materials hereinbefore named, especially for the coloration of cellulose acetate and Nylon. For the colora-e tion of organic derivative of cellulose textile materials, nuclear non-sulfonated should be employed, and it is to such compounds that our invention is more particularly directed. These compounds likewise can be used to color the other materials named herein. Nuclear sulfonated compounds of th invention, which can be prepared by sulfonation of the unsulfonated compounds, possess little or no utility for the coloration of organic derivative of cellulose textile materials but can be used to color wool and silk.

Generally speaking, the dye compounds of our invention possess exceptional light fastness properties, and as they yield valuable rubine and violet shades on cellulose acetate silk, one is able to dye this material light fast violet shades. So far as we are aware, previous attempts to secure such light fast violet shades on cellulose acetate have not been very successful. Our investiga tions lead us to believe that it is the presence of a single low carbon alkyl group, especially methyl, in the 2-position of the phenmorpholine or tetrahydroquinoline nucleus which effects such an improvement in the light fastness of the dyeings obtained. This discovery could not have been predicted.

The new azo compounds of our invention possess the further advantages of being easily dischargeable and of having superior resistance to burnt gas fumes. Other advantages include good afilnity for cellulose acetate silk and the ability to dye this material rapidly at relatively low temperatures.

The azo compounds of our invention can be prepared by diazotizing compounds having the formula N Oz-QNH:

wherein X has the meaning previously assigned to it and coupling the diazonium compounds obtained with the tetrahydroquinoline and phenmorpholine compounds indicated hereinbefore.

The following examples illustrate'the preparation of the azo compounds of our invention.

EXAMPLE 1 One gram mole of 2-amino-5-nitrophenylmethylsulfone is diazotized in an acetic acid solution of nitrosyl sulfuric acid in known manner, following which the diazonium solution obtained is poured into water and added to a cold aqueous hydrochloric acid solution of one gram mole of compounds 'line, and 1-B,- -dihydroxypropyl 2 methyl 7 chlorotetrahydroquinoline can be substituted for the coupling component of the above example to obtain dye compounds of our invention.

EXAMPLE 2 One gram mole of 2-amino-5-nitrophenylmethylsulfone is diazotized as described in Example 1, and the diazonium compound obtained is coupled with one gram mole of 1-fi,' -dihydroxypropyl-2-methyltetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors the materials named hereinbefore violet shades.

EXAMPLE 3 One grain mole of 2amino-5-nitrophenylmethylsulfone is diazotized, and the diazonium compound obtained is coupled with one gram mole of 1-fi-methyl 6,' -dihydroxypropyl-2,7-dimethyltetrahydroquinoline. Coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained yields violet shades of the materials named herein.

EXAMPLE 4 One gram mole of 2-amino-5-nitrophenylethylsulfone is diazotized, and the diazonium compound obtained is coupled with one gram mole of .1-p-hydroxyethyl-2f7-dimethyltetrahydrcquinoline. Diazotizaticn, coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors the materials previously named violet.

EXAMPLE 5 One gram mole of 2-amino-5-nitrophenylfi-methoxyethylsulfone is diazotized, and the diazonium compound obtained is coupled with one gram mole of 1-pentaerythrityl-2-methy1 tetrahydroquinoline. Diazotization, coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtainedcolors the textile materials named hereinbefore violet.

EXAMPLE 6 One gram mole of 2-amino-5-nitrophenyl-wcarboxymethylsulfone is diazotized, and the diazonium compound is coupled with one gram mole of 1-fi-hydroxyethyl-2,5 dimethylphenmorpholine. Diazotization, coupling and recovery of the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate silk bluish violet. If desired, the sodium, potassium, or triethanolamine salt, for

example, of the dye compound can be prepared by methods known to those skilled in the art. We would here note that the carboxy group attached to the methylsulfcne group may be replaced by its alkyl ester, such as the methyl or ethyl ester, or the carboxy group may be converted to its amide form or to a nitrile group.

EXAMPLE 7 one ram mole of 2-amino-5-nitropheny1-p ydroxyfl-ethoxyethylsulfone is diazotized, the diazotized JDound obtained is coupled wit one gram mole of 1'-p-methyl-fih'y-dihydroxypropyl-2,7-dimethylphenmorpho1ine. Diazotization, coupling and recoyery of the dye compound Amine Coupling component Color (1) 1-;8-hydroxyethyl-2-methyl-7-chlortetrahydroquinolin Bluish-rubine. (2) 1-fl-hydrox; propyl-2-methyltetrahydroquinoline. Violet. (3) l-'y-hyd:orvpropyLZ-methylphenmorpholine Do. (4) LB -dilly roxypropyl-Z,7-dimethylphenmrpholine.. Bluish-violet.

(5) 1-B-methylg3,' -dihydroxypropyl-2,7-dimethyltetrahydroqumolme Do. (6) 1-19,'y-dlhydi-orypropyl-2,5-dimethyltetrahydroquinoline D0. (7) l-pentaerythrityl-2,5-dimethylphenmorpholine D0. 190. (8) 119,7,6-tr1hydroXybutyl-2,7-dimethyltetrahydroquinolin D0. 2-ammo-fi-mtrophenylethylsulione 1-8 above Bluish-rubinc to bluish-violet. 2-am1no-5 I1itro-fi-methoxyethylsulfone Do. 2-amino-5-nitro-w-methoxymethylsulfone Do. 2-ammo-5-nitrophenyl-m-earbowmethylsulfone. Do. 2-amin0-5-nitrophenyl-w-carboxyethylsulionc Do.

ll l-(fi-Cll CH CONHg)-2-am1no-5-mtrobenzene. Do.

I? l-(fi-CHzC 0O CH;)-2-amino-5-11itrobenzene Do.

formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetat silk violet.

EXAMPLE 8 One gram mole of 2-amino 5-nitrophenylwmethoxymethylsulfone is diazctized, and the diazonium compound obtained is coupled with one gram mole of I-;3, ,6-trihydroxybutyl-2-methyl- 7-chlorotetrahydroquinoline. Diazotization, coupling, and recoveryof the dye compound formed can be carried out in accordance with the procedure described in Example 1. The dye compound obtained colors cellulose acetate silk deep rubine shades.

EXAMPLE 9 EXAMPLE 10 One gram mole of 2-amino-5-nitro-o-carboxamidemethylsulfone is diazotized, and the diazonium compound obtained is coupled with one gram mole of 1-5-hydroXypropyl-2-methyl-5- chlorotetrahydroquinolme. The dye compound obtained yields shades on the textile materials named heretofore.

One gram mole of diazotized 2-amino-5-nitrophenyl-e-carboxamideethylsulfone can be sub- It will be understood that the examples given are intended to be illustrative and not limitative of our invention. Thus, any of the diazonium compounds disclosed herein can be coupled with any of the coupling components indicated herein to obtain dye compounds of our invention. Additional coupling components that can be employed to prepare compounds of our invention include: 1 -,B,' -dihydroxypropyl 2 methyl 8 methoxytetrahydroquinoline l-fi,v-dihydroxypropyl 2 ethyltetrahydroquinoline 1-;8,' -dihydroxypropyl Z-p-hydroxyethyltetrahydroquinoline 1-p,' -dihydroxypropyl 2- ,8 methoxyethyltetrahydroquinoline 1-'y-hydroxypr0py1-2-methylphenmorpholine 1-o; -dihydroxypropyl-Z-methyl 7 chlorphenmorpholine 1-p-methy1li -/-dihydroxypropyl 2 propylphenmorpholine 1-ethyl-2-methy1phenmorpholine 1-propyl-2-methylphenmorpholine v 1-fi-sulfatoethyl-2-methyltetrahydroquinoline l-c-sulfoethyl-2-methylphenmorpholine 1-A-hydroxybutyl-2-methyl-5-bromotetrahydro quinoline c l l v 1-p*-hydroxyethy1-2-methyl-1-bromotetrahydroquinoline 1-p-hydroxyethyl-2-methyl 7 bromophenmorpholine 1-fl,'y-dihydroxypropyl-2-methyl 5 bromophen morpholine 1-5-sulfoethyl-2-methyltetrahydroquinoline and l-o-su-lf'atoethyl-2-methylphenmorpholine The tetrahydroquinoline coupling compounds pounds, unsubstituted in the ring nitrogen atom, and then introducing the alkyl substituent present on thering nitrogen atom by methods known to the art for their introduction. The examples given hereinafter are illustrative of the hydrogenation and alkylation reactions employed.

HYnRocENArIoN ;-Preparation of Z-methyl tetrahydroquinoline while maintaining the desired pressure, adding hydrogen until the amount required to produce the tetrahydroquinoline compound has been introduced. Again if excess hydrogen is originally added to :the pressure vessel and no further hydrogen added the reaction is complete when the pressure remains substantially constant. As will be understood, the temperature and pressure conditions employed can be varied over wide limits. Those given, however, are suitable and can be used 'to successfully hydrogenate other quinoline compounds to obtain the corresponding tetrahydroquinoline compounds.

ALKYLATION of I-a' -dihydrOmyprOpyZ-Z-methyl tetrahydroquinoline 1 gram mole of Z-methyl tetrahydroquinoline, 1.2 gram mole of sodium bicarbonate and 1.2 gram mole of glyceryl chlorohydrin are heated together in a reaction vessel with stirring at 1110? C. for five hours. Following completion of the reaction, water is added to the reaction mixture which is then steam distilled to remove any unreacted 2-methyl tetrahydroquinoline. The desired compound is then recovered from the reaction mixture in known fashion and can b used" without further purification.

Preparation of 1-,8-hydro:ryethyl-2,7-dimethyl tetrahydroquinoline 1 gram mole of 2,7-dimethyl tetrahydroquinoline is charged into an, autoclave and heated at 180 C. with 1.1 gram mole: of ethylene oxide for six hours. The reaction mixture is then permitted to cool following which the desired product is recovered by distilling the reaction mixture under reduced pressure.

The corresponding fl-hydroxyl propyl compound can be similarly prepared by using propylene oxide in place of ethylene oxide.

Preparation of 1-sodiam-p-salfoethyZJ-chlorotetrahydroquinoline .1 gram mole of '7-chlorotetrahydroquinoline, 1.1 gram mole of sodium-13-bromoethanesulfonate and 1.1 gram mole of sodium bicarbonate are heated together in a suitable reaction vessel to 120150 C. for several hours. When no more carbon dioxide is evolved, the reaction mixture is poured intovwater, steam distilled to remove unreacted 7-chlorotetrahydroquinoline and the remaining. solution concentrated to produce r stall z ion 1 the s r p d Preparation The'phenmorpholine coupling compounds employed inthe preparation of the azo-compounds of .our invention can be prepared by alkylation ofthe corresponding phenmorpholine compounds which are unsubstituted in the ring nitrogen atom. Alkylation can be carried out in the same manner as described for the tetrahydroquinoline compounds and is illustrated by the following examples.

Preparation 1 of 1 -hydromypropyl-z-methyl phenmorpholine 12 gram mole of-2-methyl phenmorpholine is reacted with 1.1 gram mole of trimethylene chlorohydrin and 0.6 gram mole of sodium carbonate in a suitable reaction vessel at 140 C. for five hours. The desired product may be recovered from the reaction mixture by distillation under reduced pressure.

Preparation of 1-sodiam-,3-saZfatoethyl-2,7- dimethyl phenmorpholine 1 gram mole of 1-p-hydroxyethyl-2,7-dimethylphenmorpholine are dissolved in carbon tetrachloride and 1 gram mole of chlorosulfonic acid is added and the reaction conducted without heating; the reaction being completed by warming slightly. Sodium carbonate is then added to the reaction mixture until it is neutral to Congo red paper. The carbon tetrachloride may be largely removed by distillation following which the desired product can be obtained by crystallization on evaporation of the remaining carbon tetrachloride.

Additional information regarding the preparation of phenmorpholine compounds is to be found in McNally and Dickey U. S. Patent No. 2,196,222,

issued April 9, 1940. Similarly, additional information concerning the preparation of tetrahydroquinoline compounds will be found in Dickey andMcNally application Serial No. 306,201, filed November 25, 1939.

The azo compounds of our invention are, for the most part; relatively insoluble in water'and',

accordingly, they can be advantageously directly applied to the material undergoing colorationin the form of an aqueous suspension which can be prepared by grinding the dye to a paste in the presence of a sulfonated oil, soap'or other suitable dispersing agent and dispersing the resulting paste in water. In some instances, the dye may possess sufiicient solubility in water as to render the use of a dispersing agent unnecessary; Generally speaking, however, the use of a dispersing agent is desirable.

Direct dyeing operations can, withadvantage, be conducted at temperatures of about 75-85" C.

but any suitable temperature may be used. Thus,"

the textile material to be dyed or colored is ordinarily added to the dyebath at a temperature lower than that at which the main portion of the dye is tobe effected, a temperature ap-' proximating 45-55 C.,- for example, following.

which the temperature is raised to that selected for carrying out the dyeing operation. The temperature at which the dyeing is conducted may, of course, be varied somewhat depending upon the particular material undergoing coloration. As is understood by those skilled in the art, the intensity 'of dyeing can be varied by varying theproportion of dye to material undergoing color-'- ation. Generally speaking, 1-3% by weight ofdye to material is employed although any desired proportions can be used.

Suitable dispersing agents together with the amounts that may be employed are disclosed in McNally and Dickey Patent No. 2,115,030, issued April 26, 1938. The process disclosed in this patent for the dyeing of cellulose acetate silk can be used in applying the dyes of the present application to this material.

It will be understood that the other textile materials named hereinbefore can be directly colored from an aqueous dyebath in a similar manner as cellulose acetate silk. However, other suitable methods for the dyeing of these materials are known to those skilled in the art and these methods, of course, can be used in applying the dye compounds of this application if desired. We would further note that, while colors yielded by the dye compoundshave been given primarilywith reference to cellulose acetate silk, generally similar colors are ordinarily obtained on the other materials.

We claim:

1. The azo compounds having the formula:

wherein X stands for a member selected from the group consisting of an alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group,

and R1 stands for a member selected from the group consisting of a l-alkyl-Z-low carbon alkyl tetrahydroquinoline nucleus and a 1-a1kyl-2-low carbon alkyl phenmorpholine nucleus, said tetrahydroquinoline and phenmorpholine nuclei being joined to the azo bond shown through the carbon atom in the 6-position.

2. The azo compounds having the formula:

wherein X stands for a member selected from the group consisting of a alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group, and R1 stands for a l-hydroxyalkyl-2-low carbon alkyl phenmorpholine nucleus which is joined to the azo bond shown through the carbon atom in its d-position.

4. The azo compounds having the formula:

allkyl Y- 0-12, NOPON=N Q O=fiX Y1 wherein Q stands for a member selected from the group consisting of O and CH2, R2 stands for a low carbon alkyl group, X stands for a member selected from the group consisting of an alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group, and Y and Y1 each stands for a member selected from the group consisting of hydrogen, a low carbon alkyl hydrocarbon group and a halogen atom.

5. The azo compounds having the formula:

lliydroxyalkyl N H Y on;

wherein Q stands for a memberselected from the" group consisting of O and CH2 and Y and Y1 each stands for a member selected from the group consisting of hydrogen, a low carbon alkyl hydro carbon group, and a halogen atom.

'7. The azo compounds having the formula:

wherein R3 stands for a fiky-dihydroxypropyl group, Q stands for a member selected from the group consisting of O and CH2 and Y and Y1 each stands for a member selected from the group consisting of hydrogen, a low carbon alkyl hydrocarbon group, and a halogen atom.

8. The azo compounds having the formula:

wherein R3 stand for a p;y-dihydroxypropyl group and Y and Y1 each stands for a member selected from the group consisting of hydrogen, a. low carbon alkyl hydrocarbon group and a halogen atom.

t 9. The azo compounds having the formula:

wherein R3 stands for a fln-dihydroxypropyl group and Y and Y1 each stands for a member selected from the group consisting of hydrogen, a low carbon alkyl hydrocarbon group, and a halogen atom.

10. The azo compound having the formula:

' CHaCHOHCHiOH I 11. The azo compound having the formula:

' omononomon 12. Textile material colored with an 2.20 com- Pound having the formula:

f sash:

wherein X stands for a member selected from the group consisting of an alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group, and R1 stand for a member selected from the group consisting of a 1-alkyl-2-low carbon alkyl tetrahydroquinoline nucleus and a 1-alky1-2-low carbon alkyl phenmorpholine nucleus, said tetrahydroquinoline and phenmorpholine nuclei being joined to the azo bond shown through the carbon atom in the 6,-position.

13.- Textile material colored with an azo dye compound having the formula:

hydroxyelkyl wherein X stands for a member selected from the group consisting of an alkyl group, an alkylcarboxyl group, and an alkylcarboxamide group, and R1 stands for a member selected from the group consisting of a l-alkyl-Z-low carbon alkyl tetrahydroquinoline nucleus and a 1-alkyl-2-low carbon alk'yl phenmorpholine nucleus, said tetrahydroquinoline and phenmorpholine nuclei being joined to. the azo bond shown through the carbon atom in the 6-position.

15. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the formula:

hydroxyalkyl wherein-Q stands for a member selected from the group consisting of O and CH2 and Y, and Y1 each stands for a member selected from the group consisting of hydrogen, a low carbon alkyl hydrocarbon group, and a halogen atom.

JOSEPH B. DICKEY. JAMES G. McNALLY. 

